1. Technical Field
This invention relates to an insecticidal and acaricidal agent which contains an anilinopyrimidinone derivative as an active ingredient. Particularly, it relates to an insecticidal and acaricidal agent which is effective for controlling insect pests of agricultural and horticultural products.
2. Background Art
In the field of agriculture and horticulture, various insecticides have been developed and put into practical use for the purpose of controlling various types of disease and insect damage. However, the generally used insecticides for agricultural and horticultural use are not always satisfactory in terms of their insecticidal effect, insecticidal spectrum or residual effect. Also, it cannot be said that they satisfy certain requirements such as reduction of the number of times of application and of the amount of a chemical to be applied.
In addition, there is a problem regarding the generation of disease and insect pests which acquired resistance to generally used agricultural chemicals. For example, in the case of the cultivation of crops such as vegetables, fruit trees, flowers and ornamental plants, tea plants, wheat and related crops and rice plants, various disease and insect pests which acquired resistance to various types of agricultural chemicals such as of triazole, imidazole, pyrimidine, benzimidazole, dicarboxyimide, phenylamide and organic phosphate systems have been found in various districts, and difficulty in preventing these disease and insect pests has been increasing every year.
Though there are certain agricultural chemicals which are not possessed of the resistance to disease and insect pests yet (e.g., dithiocarbamate and phthalimide agricultural chemicals), these chemicals are not desirable from the viewpoint, for example, of environmental pollution because of their generally large amount to be applied and application times. In consequence, great concern has been directed toward the development of a novel insecticide which can show sufficient preventive activity with a low applying amount upon various disease and insect pests which acquired resistance to the general agricultural and horticultural insecticides and also has less bad influence upon the natural environment. Regarding the acaricides, great concern has also be directed toward the development of an acaricide which shows excellent preventive activity upon mites having resistance to generally used acaricides and has high safety.
2-Arylaminopyrimidinone derivatives having herbicidal activities and plant growth regulator actions have been disclosed in WO 93/21162 (an unexamined published Japanese patent application No. 6-321913). However, the just described document does not describe about physiological activities of these compounds other than their herbicidal activities and plant growth regulator actions, such as insecticidal and acaricidal activities.
The inventors of the present invention have conducted intensive studies searching for an insecticidal and acaricidal agent which shows high preventive activity upon various disease and insect pests having resistance to the conventional insecticides and acaricides for agricultural and horticultural use and also has high safety with alleviated problems such as residual toxicity and environmental pollution, and have found as a result of the efforts that an anilinopyrimidinone derivative having a specified structure is a compound having the aforementioned characteristics, thus resulting in the accomplishment of the present invention.
Accordingly, the present invention relates to an insecticidal and acaricidal agent which contains, as an active ingredient, an anilinopyrimidinone derivative represented by a general formula (I) 
(wherein R1 represents a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a (C1-C4 alkoxy)C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C5 acyl group, a (C1-C4 alkoxy)carbonyl group, a C3-C6 alkenyl group, a C3-C6 alkenyloxy group, a C3-C6 alkynyl group, a C3-C6 alkynyloxy group, a C1-C5 acyloxy group, a (C1-C4 alkoxy)C1-C4 alkoxy group, a carboxy(C1-C4 alkyl) group, a (C1-C4 alkoxy)carbonyl(C1-C4 alkyl) group, a carboxy(C1-C4 alkoxy) group, a (C1-C4 alkoxy)carbonyl(C1-C4 alkoxy) group, a C1-C4 alkylamino group, a di(C1-C4 alkyl)amino group, a C1-C5 acylamino group, a C1-C4 alkylsulfonylamino group, a mercapto group, a cyano group, a carboxy group, an amino group or a hydroxyl group, m is an integer of from 1 to 5, with the proviso that R1 may be the same or different from each other when m is an integer of from 2 to 5, R2 represents a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C3-C6 alkynyl group, a C1-C6 haloalkyl group, a (C1-C4 alkoxy)C1-C4 alkyl group, a C1-C4 alkoxy(C1-C4 alkoxy)C1-C4 alkyl group, a (C1-C4 haloalkoxy)C1-C4 alkyl group, a (C1-C4 alkylthio)C1-C4 alkyl group, a carboxy(C1-C4 alkyl) group, a (C1-C4 alkoxy)carbonyl(C1-C4 alkyl) group, a (C1-C4 alkoxy)carbonyloxy(C1-C4 alkyl) group, a (C1-C5 acyloxy)C1-C4 alkyl group, a cyano(C1-C4 alkyl) group, a cyanothio(C1-C4 alkyl) group, a C1-C5 acyl group, a (C1-C4 alkoxy)carbonyl group, an aminocarbonyl group, a (C1-C6 alkyl)aminocarbonyl group, a di(C1-C6 alkyl)aminocarbonyl group, a (C1-C6 alkyl)sulfonyl group, a benzenesulfonyl group which may be substituted or a C7-C8 aralkyl group which may be substituted, R3 represents a hydrogen atom, a C1-C6 alkyl group, a C3-C6 alkenyl group, a C3-C6 alkynyl group, a C3-C7 cycloalkyl group or an amino group, X represents a halogen atom, a C1-C4 alkyl group or a C1-C4 haloalkyl group, and Y represents a hydrogen atom or a halogen atom).
In the anilinopyrimidinone derivative represented by the general formula (I) as the active ingredient of the insecticidal and acaricidal agent of the present invention, illustrative examples of R1 include hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl; alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy; alkoxyalkyl groups such as methoxymethyl, 2-methoxyethyl, ethoxymethyl and 2-ethoxyethyl; haloalkyl groups such as fluoromethyl, chloromethyl, bromomethyl, trichloromethyl, trifluoromethyl, 1-chloroethyl, 2-chloroethyl and 3-chloropropyl; haloalkoxy groups such as trifluoromethoxy, difluoromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloro-1-methylethoxy and 2,2,2-trifluoroethoxy; alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio and tert-butylthio; alkylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl and tert-butylsulfinyl; alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and tert-butylsulfonyl; acyl groups such as formyl, acetyl, propionyl, butyryl, valeryl and pivaloyl; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl; alkenyl groups such as 2-propenyl and 3-methyl-2-propenyl; alkenyloxy groups such as 2-propenyloxy and 2-butenyloxy; alkynyl groups such as propargyl, 2-butinyl and 1-butin-3-yl; alkynyloxy groups such as 2-propynyloxy and 1-methyl-2-propynyloxy; acyloxy groups such as acetoxy and propionyloxy; alkoxyalkoxy groups such as methoxymethoxy, ethoxymethoxy, isopropoxymethoxy and 2-methoxyethoxy; carboxyalkyl groups such as carboxymethyl and 1-(carboxy)ethyl; alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl and 1-(methoxycarbonyl)ethyl; carboxyalkoxy groups such as carboxymethoxy and 1-(carboxy)ethoxy; alkoxycarbonylalkoxy groups such as methoxycarbonylmethoxy, ethoxycarbonylmethoxy and 1-(methoxycarbonyl)ethoxy; alkylamino groups such as methylamino, ethylamino, propylamino, isopropylamino and butylamino; dialkylamino groups such as dimethylamino, diethylamino and methylpropylamino; acylamino groups such as acetylamino and propionylamino; alkylsulfonylamino groups such as methylsulfonylamino and ethylsulfonylamino; mercapto group; cyano group; carboxy group; amino group; and hydroxyl group.
Illustrative examples of R2 in the general formula (I) include hydrogen atom; alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl; alkenyl groups such as 2-propenyl and 2-butenyl; alkynyl groups such as propargyl, 1-butin-3-yl and 2-butinyl; haloalkyl groups such as chloromethyl, trichloromethyl, 2-chloroethyl and 3-fluoropropyl; alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, propyloxymethyl, butyloxymethyl, 1-methoxyethyl and 2-methoxyethyl; alkoxyalkoxyalkyl groups such as 2-methoxyethoxymethyl and 2-ethoxyethoxymethyl; haloalkoxyalkyl groups such as trichloromethoxymethyl and trifluoromethoxymethyl; alkylthioalkyl groups such as methylthiomethyl, ethylthiomethyl, 1-(methylthio)ethyl and 2-(methylthio)ethyl; carboxyalkyl groups such as carboxymethyl, 1-(carboxy)ethyl and 2-(carboxy)ethyl; alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl, propyloxycarbonylmethyl, isopropyloxycarbonylmethyl, 1-(methoxycarbonyl)ethyl, 2-(methoxycarbonyl)ethyl and 1-(methoxycarbonyl)propyl; alkoxycarbonyloxyalkyl groups such as methoxycarbonyloxymethyl, ethoxycarbonyloxymethyl, isopropyloxycarbonyloxymethyl and 1-(methoxycarbonyloxy)ethyl; acyloxyalkyl groups such as formyloxymethyl, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl and pivaloyloxymethyl; cyanoalkyl groups such as cyanomethyl and 1-cyanoethyl; cyanothioalkyl groups such as cyanothiomethyl; acyl groups such as formyl, acetyl, propionyl, butyryl, valeryl and pivaloyl; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl and tert-butoxycarbonyl; carbamoyl group; alkylaminocarbonyl groups such as methylcarbamoyl, ethylcarbamoyl and cyclohexylcarbamoyl; dialkylaminocarbonyl groups such as dimethylcarbamoyl, diethylcarbamoyl, ethylpropylcarbamoyl, cyclohexylethylcarbamoyl, 1-pyrrolidinylcarbonyl, piperidinocarbonyl and morpholinocarbonyl; alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, butylsulfonyl and isobutylsulfonyl; benzenesulfonyl groups which may be substituted, such as benzenesulfonyl and p-toluenesulfonyl; and aralkyl groups which may be substituted, such as benzyl, 4-chlorobenzyl, 4-fluorobenzyl, 4-methylbenzyl, 4-trifluoromethylbenzyl, 4-methoxybenzyl, xcex1-phenethyl and xcex2-phenethyl.
Illustrative examples of R3 in the general formula (I) include hydrogen atom; alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl and hexyl; alkenyl groups such as 2-propenyl and 2-butenyl; alkynyl groups such as propargyl, 2-butinyl and 1-butin-3-yl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and amino group.
Illustrative examples of X in the general formula (I) include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl; and haloalkyl groups such as trichloromethyl, trifluoromethyl and 2,2,2-trifluoroethyl; and examples of Y include hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom.
Among anilinopyrimidinone derivatives represented by the general formula (I), a preferred compound from the viewpoint of insecticidal and acaricidal activities is an anilinopyrimidinone derivative in which R1 is a halogen atom or a haloalkyl group, R2 is hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkylthioalkyl group, an acyloxyalkyl group, an alkoxycarbonyl group or an alkylsulfonyl group, R3 is an alkyl group, an alkenyl group or a cycloalkyl group, X is a halogen atom or a haloalkyl group, Y is hydrogen atom or a halogen atom and m is from 1 to 3. Particularly, among anilinopyrimidinone derivatives in which X is trifluoromethyl group, an anilinopyrimidinone derivative in which R1 is chlorine atom or trifluoromethyl group, m is 2 or 3 and Y is hydrogen atom or chlorine atom is preferred in view of its strong insecticidal and acaricidal activities.
Though most of the anilinopyrimidinone derivatives represented by the general formula (I) are compounds which are included in the general formula described in WO 93/21162, the specification of this WO 93/21162 does not describe insecticidal activity and acaricidal activity of these compounds. In addition, WO 93/21162 discloses a general formula which includes a markedly broad range of compounds, but only a part of these compound are actually synthesized and checked for their herbicidal or plant growth regulating activity.
Among the anilinopyrimidinone derivatives of the present invention having excellent effect as an insecticidal and acaricidal agent, an anilinopyrimidinone derivative represented by the following general formula (II) 
(wherein R11 represents chlorine atom or trifluoromethyl group, n is 1 or 2, wherein R11 may be the same or different from each other when n is 2, R21 represents a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C3-C6 alkynyl group, a C1-C6 haloalkyl group, a (C1-C4 alkoxy)C1-C4 alkyl group, a C1-C4 alkoxy(C1-C4 alkoxy)C1-C4 alkyl group, a (C1-C4 haloalkoxy)C1-C4 alkyl group, a (C1-C4 alkylthio)C1-C4 alkyl group, a carboxy(C1-C4 alkyl) group, a (C1-C4 alkoxy)carbonyl(C1-C4 alkyl) group, a (C1-C4 alkoxy)carbonyloxy(C1-C4 alkyl) group, a (C1-C5 acyloxy)C1-C4 alkyl group, a cyano(C1-C4 alkyl) group, a cyanothio(C1-C4 alkyl) group, a C1-C5 acyl group, a (C1-C4 alkoxy)carbonyl group, an aminocarbonyl group, a (C1-C6 alkyl)aminocarbonyl group, a di(C1-C6 alkyl)aminocarbonyl group, a (C1-C6 alkyl)sulfonyl group, a benzenesulfonyl group which may be substituted or a C7-C8 aralkyl group which may be substituted, R31 represents a C1-C6 alkyl group, a C3-C6 alkenyl group or a C3-C7 cycloalkyl group, and Y1 represents a hydrogen atom or a halogen atom) is a novel compound which is not illustratively shown in WO 93/21162.
Production method of the anilinopyrimidinone derivative of general formula (I) is not particularly limited, and it can be produced, for example, by the following production methods. 
(In the above reaction formula, R is a C1-C6 alkyl group, p is 0 or 2, Xxe2x80x2 is a C1-C4 alkyl group or a C1-C4 haloalkyl group, and R1, R3 and m are as defined in the foregoing.) 
(In the above reaction formula, R is a C1-C6 alkyl group, Z is a halogen atom, Xxe2x80x2 is a C1-C4 alkyl group or a C1-C4 haloalkyl group, and R1, R3 and m are as defined in the foregoing.)
In the step 1 of the production methods 1 and 2, a compound in which X of the anilinopyrimidinone derivative (I) is a C1-C4 alkyl group or a C1-C4 haloalkyl group, namely the anilinopyrimidinone derivative (Ia), is produced by using a 2-alkylthiopyrimidinone or 2-alkylsulfonylpyrimidinone derivative (III) or a 2-halogenopyrimidinone derivative (VI) as a starting material and allowing the material to react with anilines (IV).
It is desirable to carry out the reaction of step 1 in the presence of a base, in view of high yield. Illustrative examples of the base include alkali metal bases such as sodium hydride, potassium hydride, lithium amide, sodium amide, lithium diisopropylamide, butyl lithium, tert-butyl lithium, trimethysilyl lithium, lithium hexamethyldisilazide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide and potassium tert-butoxide, and organic bases such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine, diazabicycloundecene, diazabicyclooctane and imidazole. The compound of interest can be obtained with a high yield when the base is used in an amount of from 0.1 to 2.0 equivalents based on the substrate.
This reaction can be carried out in a solvent, and any solvent which does not spoil the reaction can be used. Examples of the reaction-inert solvent include amide solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene, aliphatic hydrocarbon solvents such as pentane, hexane and octane, ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), dimethoxyethane (DME) and 1,4-dioxane, and dimethylsulfoxide (DMSO), or mixed solvents thereof.
The compound of interest can be obtained with a high yield by carrying the reaction at a temperature optionally selected within the range of from xe2x88x9278 to 100xc2x0 C.
In the production method 1, the 2-alkylthiopyrimidinone derivative to be used as the starting material can be produced easily by carrying out cyclization condensation reaction of a 3-aminoacrylic acid ester derivative with isothiocyanates in accordance with a known method (e.g., WO 93/21162). Also, the 2-alkylsulfonylpyrimidinone derivative can be produced by oxidizing the 2-alkylthiopyrimidinone derivative. In addition, the 2-halogenopyrimidinone derivative (VI) to be used as the starting material in the production method 2 can be produced easily by carrying out chlorination of the 2-hydroxypyrimidinone derivative (V) which can be produced easily by the cyclization condensation reaction of a xcex2-keto ester derivative with isocyanates, using a halogenation agent such as phosphorus pentachloride, phosphorus oxytrichloride, phosphorus pentabromide or phosphorus oxytribromide. 
(In the above reaction formula, Z is a halogen atom, and R1, R3, X and m are as defined in the foregoing.)
In the step 2 of production method 3, the anilinopyrimidinone derivative (Iaxe2x80x2) is produced by allowing a 2-aminopyrimidinone derivative (VII) to react with a halobenzene derivative (VIII) having an activated halogen atom, in the presence of a base.
It is desirable to carry out the reaction in the presence of a base in view of high yield. Examples of the base include organic bases such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine, diazabicycloundecene, diazabicyclooctane and imidazole, and alkali metal bases such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyl lithium, tert-butyl lithium, lithium diisopropylamide, trimethylsilyl lithium and lithium hexamethyldisilazide. The compound of interest can be obtained with a high yield when the base is used in an amount of from 1 to 1.5 equivalents based on the substrate.
It is desirable to carry out this reaction in a solvent. As the solvent, any solvent which does not spoil the reaction can be used, and its examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene, aliphatic hydrocarbon solvents such as pentane, hexane and octane, ether solvents such as diethyl ether, diisopropyl ether, THF, DME and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone and cyclohexanone, halogenated solvents such as chloroform and dichloromethane, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, amide solvents such as DMF, N,N-dimethylacetamide and N-methylpyrrolidone, and DMSO, or mixed solvents thereof.
Though it varies depending on the base used and reaction conditions, this reaction can be carried out at a temperature optionally selected within the range of from 0xc2x0 C. to reflux temperature of the solvent used.
Some of the 2-aminopyrimidinone derivatives (VII) to be used in this step are on the market and easily available, but can also be produced easily by allowing an xcex1-keto ester derivative to react with substituted or unsubstituted guanidine. Also, the halobenzene derivative (VIII) is on the market and easily available. In addition, in the halobenzene derivative (VIII) to be used in this reaction, the halogen atom represented by Z is preferably fluorine atom or bromine atom in view of high reaction yield, and the substituent R1 on the phenyl ring is preferably an electron-withdrawing group such as a halogen atom, trichloromethyl group, trifluoromethyl group or a cyano group, which can activate the halogen atom more effectively. 
(In the above reaction formula, Yxe2x80x2 is a halogen atom, R2xe2x80x2 is any one of the substituents represented by R2, excluding hydrogen atom, L is a leaving group, and R1, R3, X and m are as defined in the foregoing.)
In the production method 4, anilinopyrimidinone derivatives (Ib, Ic and Id) are produced by halogenation (step 3) of the 5-position, and alkylation (step 4) on the nitrogen atom of the anilino group at the 2-position, of the anilinopyrimidinone derivative (Ia) obtained in the production methods 1 to 3.
In the step 3, the 5-position of the pyrimidine ring of the anilinopyrimidinone derivative (Ia) or (Ic) is halogenated to produce the corresponding anilinopyrimidinone derivative (Ib) or (Id).
The halogenation can be carried out using a halogenation agent, and examples of the useful halogenation agent include chlorine, bromine, iodine, potassium fluoride, sulfuryl chloride, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, tert-butyl hypochlolite, diethylaminosulfa trifluoride, carbon tetrachloride/triphenylphosphine and carbon tetrabromide/triphenylphosphine.
This reaction can be carried out in a solvent which does not spoil the reaction, and its examples include aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene, aliphatic hydrocarbon solvents such as pentane, hexane and octane, ether solvents such as diethyl ether, diiospropyl ether, THF, DME and 1,4-dioxane, halogenated solvents such as chloroform, methylene chloride and carbon tetrachloride and organic acid solvent such as acetic acid and propionic acid, or mixed solvents thereof.
The compound of interest can be obtained with a high yield by carrying the reaction at a temperature optionally selected within the range of from 0 to 100xc2x0 C.
In the step 4, the anilinopyrimidinone derivative (Ia) or (Ib) is used as the starting material and allowed to react with a substance represented by a general formula R2xe2x80x2-L in the presence of a base to produce the corresponding anilinopyrimidinone derivative (Ic) or (Id).
This reaction is carried out in the presence of a base. Examples of the base include alkali metal bases such as sodium hydride, potassium hydride, lithium amide, sodium amide, lithium diisopropylamide, butyl lithium, tert-butyl lithium, trimethylsilyl lithium, lithium hexamethyldisilazide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide and potassium tert-butoxide, and organic bases such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine, diazabicycloundecene, diazabicyclooctane and imidazole. The compound of interest can be obtained with a high yield when the base is used in an amount of from 1 to 2 equivalents based on the substrate.
This reaction can be carried out in a solvent which does not spoil the reaction. Examples of the solvent include amide solvents such as DMF, N,N-dimethylacetamide and N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, aromatic hydrocarbon solvents such as benzene, toluene, xylene and chlorobenzene, aliphatic hydrocarbon solvents such as pentane, hexane and octane, ether solvents such as diethyl ether, diisopropyl ether, THF, DME and 1,4-dioxane, and DMSO, or mixed solvents thereof.
The compound of interest can be obtained with a high yield by carrying the reaction at a temperature optionally selected within the range of from 0 to 100xc2x0 C.
In this reaction, the compound of interest can be obtained with more higher yield by the use of a catalyst, and its examples include polyethers such as 18-crown-6, 15-crown-5 and 12-crown-4 and quaternary ammonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide, triethylbenzylammonium chloride, tetrabutylammonium sulfate and tetraethylammonium iodide.
Regarding the substance (R2xe2x80x2-L) to be used in this step, examples of the substituent represented by R2xe2x80x2 are as described in the foregoing, and examples of the leaving group represented by L include halogen atoms such as chlorine atom, bromine atom and iodine atom and substituted sulfonyloxy groups such as methanesulfonyloxy group, benzenesulfonyloxy group and p-toluenesulfonyloxy group. In consequence, illustrative examples of the substance represented by the general formula R2xe2x80x2-L include methyl bromide, methyl iodide, ethyl bromide, isopropyl iodide, allyl chloride, allyl bromide, methallyl chloride, allyl methanesulfonate, propargyl bromide, propargyl p-toluenesulfonate, 1-butin-3-yl p-toluenesulfonate, difluorochloromethane, 1-bromo-3-fluoropropane, 3,3,3-trifluoropropyl iodide, chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl propyl ether, chloromethyl isopropyl ether, chloromethyl butyl ether, chloromethyl isobutyl ether, chloromethyl (methoxyethyl) ether, chloroethyl (chloromethyl) ether, chloromethyl methyl thioether, chloroacetic acid, bromoacetic acid, xcex1-chloropropionic acid, methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate, isopropyl bromoacetate, methyl xcex1-chloropropionate, ethyl xcex1-chloropropionate, ethyl(1-chloroethyl) carbonate, ethyl(1-bromoethyl) carbonate, chloromethyl acetate, (1-chloroethyl) acetate, (bromomethyl) acetate, chloroacetonitrile, xcex1-chloropropionitrile, cynaothiomethyl chloride, cyanothiomethyl bromide, acetyl chloride, acetyl bromide, propionyl chloride, butyryl chloride, valeryl chloride, pivaloyl chloride, methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, isobutyl chloroformate, tert-butyl chloroformate, methylcarbamoyl chloride, ethylcarbamoyl chloride, isopropylcarbamoyl chloride, butylcarbamoyl chloride, sec-butylcarbamoyl chloride, cyclohexylcarbamoyl chloride, dimethylcarbamoyl chloride, diethylcarbamoyl chloride, diisopropylcarbamoyl chloride, methylethylcarbamoyl chloride, ethylpropylcarbamoyl chloride, ethylcyclohexylcarbamoyl chloride, methylsulfonyl chloride, ethylsulfonyl chloride, isopropylsulfonyl chloride, isobutylsulfonyl chloride, phenylsulfonyl chloride, p-toluenesulfonyl chloride, 4-fluorophenylsulfonyl chloride, 4-chlorophenylsulfonyl chloride, benzyl chloride, benzyl bromide, 4-fluorobenzyl chloride, 4-fluorobenzyl bromide, 4-methoxybenzyl chloride, 4-methoxybenzyl bromide, 3,4-dimethoxybenzyl chloride and xcex1-phenethyl chloride. In addition, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate and xcex1,xcex1-dihaloalkanes such as dibromomethane and chlorobromomethane as described below are also included in the substance (R2xe2x80x2-L).
In addition to the aforementioned means, the intended anilinopyrimidinone derivative (Ic) or (Id) can be produced in the step 4 by a method exemplified in the following. That is, by using an xcex1,xcex1-dihaloalkane such as dibromomethane or chlorobroanomethane as the substance and allowing it to react with the anilinopyrimidinone derivative (Ia) or (Ib) in the presence of a base such as sodium hydride or sodium amide, the nitrogen atom of 2-anilino group can be 1-bromoalkylated or 1-chloroalkylated. This reaction can be carried out in an ether solvent such as THF or DME at a reaction temperature of approximately from 0 to 50xc2x0 C. Though these haloalkyl compounds can be isolated if desired, the anilinopyrimidinone derivative (Ic) or (Id) in which the nitrogen atom of 2-anilino group is alkoxyalkylated or alkylthioalkylated can be produced by allowing these compounds in the reaction system, without isolation, to react with an alkali metal alkoxide or thioalkoxide such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium thiomethoxide or sodium thioethoxide. This reaction can be carried out in an ether solvent such as THF or DME at a reaction temperature selected within the range of from room temperature to reflux temperature of the solvent used.
In addition, in the step 4, the anilinopyrimidinone derivative (Ic) or (Id) is which the nitrogen atom of 2-anilino group is alkoxymethylated can be produced by allowing the anilinopyrimidinone derivative (Ia) or (Ib) and a dialkoxymethane such as dimethoxymethane or diethoxymethane to react with Vilsmeier""s reagent in an organic solvent and then treating the resulting product with a tertiary amine. This reaction can be carried out in an aromatic hydrocarbon solvent such as benzene, toluene, xylene or chlorobenzene at a reaction temperature selected within the range of from 0 to 100xc2x0 C. The Vilsmeier""s reagent can be prepared from phosphorus oxychloride, thionyl chloride or phosgene and DMF, but it is desirable to use phosphorus oxychloride in view of high yield. Regarding the tertiary amine, amines such as triethylamine, tripropylamine, tributylamine, N-methylmorpholine and N,N-dimethylaniline can be used.
The anilinopyrimidinone derivative represented by the general formula (I) shows high preventive activity at a low chemical concentration upon insanitary insects or insect pests harmful to the agricultural and horticultural products, particularly upon insects and mites. Examples of the insect pests and mites to be controlled include larvae and imagoes of insects belonging to Lepidoptera such as common cutworm, diamondback moth, smaller tea tortrix, grass leaf roller and rice stem borer; belonging to Hemiptera including rice insects such as brown rice planthopper and white-backed planthopper, leafhoppers such as green rice leafhopper and tea green leafhopper, aphids such as green peach aphid and cotton aphid, whiteflies such as greenhouse whitefly and stink bugs such as a green stink bug; belonging to Coleoptera such as striped flea beetle, cucurbit leaf beetle and adzuki bean weevil; belonging to Diptera such as housefly and common gnat; and belonging to Orthoptera such as a cockroach (Periplaneta americana), and eggs and imagoes of mites belonging to Acarina such as two-spotted spider mite, citrus red mite, Japanese citrus rust mite and broad mite. In consequence, the anilinopyrimidinone derivative (I) is useful as an insecticide and an acaricide for agricultural and horticultural use. As a matter of course, the insects and mites to be controlled by the insecticidal and acaricidal agent of the present invention are not limited to the just exemplified cases.
When the anilinopyrimidinone derivative represented by the general formula (I) is used as agricultural and horticultural insecticide and acaricide, it may be used alone but preferably in the form of a composition produced using a general agricultural adjuvant. Though the form of the insecticidal and acaricidal agent of the present invention is not particularly limited, it is desirable to make it into, for example, emulsifiable concentrates, wettable powders, dusts, flowables, fine granules, granules, tablets, oil solutions, propellents or aerosols. One or more members of the anilinopyrimidinone derivative (I) can be formulated as active ingredients.
The agricultural adjuvant to be used for the production of an insecticidal and acaricidal agent can be used for the purpose, for example, of improving and stabilizing the insecticidal and acaricidal effects and improving the dispersibility. For example, a carrier (diluent), a spreader, an emulsifier, a wetting agent, a dispersing agent and a disintegrating agent can be used.
Examples of the liquid carrier include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone and cyclohexanone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, cyclohexane, animal and plant oils and fatty acids. Examples of the solid carrier include clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch and gum arabic.
Regarding the emulsifier and dispersing agent, conventional surfactants can be used, which include anionic, cationic, nonionic and amphoteric surfactants, such as sodium higher alcohol sulfate, strearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether and laurylbetaine. Also useful are spreaders such as polyoxyethylene nonylphenyl ether and polyoxyethylene laurylphenyl ether; wetting agents such as dialkyl sulfosuccinate; adhesive agents such as carboxymethylcellulose and polyvinyl alcohol; and disintegrating agents such as sodium lignin sulfonate and sodium lauryl sulfate.
Amount of the active ingredient in the insecticidal and acaricidal agent for agricultural and horticultural use is selected within the range of from 4.1 to 99.5% and optionally decided depending on various conditions such as formulation types and application methods, and it is desirable to produce the agent in such a manner that is contains the active ingredient in an amount of approximately from 0.5 to 20% by weight and preferably from 1 to 10% by weight in the case of dusts, approximately from 1 to 90% by weight and preferably from 10 to 80% by weight in the case of wettable powder or approximately from 1 to 90% by weight and preferably from 10 to 40% by weight in the case of emulsifiable concentrates.
For example, in the case of the emulsifiable concentrate, a formulated concentrate of the emulsifiable concentrate can be produced by mixing the anilinopyrimidinone derivative (I) with a solvent and an additive (e.g., surfactant), and the formulated concentrate can be applied by diluting it with water to a predetermined concentration when used. In the case of the wettable powder, a formulated concentrate can be produced by mixing the aforementioned compound as the active ingredient with a solid carrier and an additive (e.g., a surfactant), and the thus formulated concentrate can be applied by diluting it with water to a predetermined concentration when used. In the case of the dust, it can be produced by mixing the active ingredient anilinopyrimidinone derivative (I) with a solid carrier and necessary additives and applied as such, and in the case of the granule, it can be produced by mixing the active ingredient anilinopyrimidinone derivative (I) with a solid carrier, a surfactant and necessary additives and making the mixture into granules which can be applied as such. As a matter of course, production methods of the aforementioned formulation types are not limited to those exemplified in the above and can be selected optionally by those skilled in the art depending on the types of the active ingredient, application purpose and other conditions.
In addition to the anilinopyrimidinone derivative represented by the general formula (I) as the active ingredient, the insecticidal and acaricidal agent of the present invention for agricultural and horticultural use may be formulated with other optional active ingredients such as a fungicide, an insecticide, an acaricide, a herbicide, an insect growth controlling agent, a fertilizer and a soil conditioner. Application method of the insecticidal and acaricidal agent of the present invention for agricultural and horticultural use is not particularly limited, and it can be applied by any of the usual methods such as foliar application, submerged application, soil treatment and seed treatment. For example, in the case of the foliar application, a solution containing from 5 to 1,000 ppm, preferably from 10 to 500 ppm, of the active ingredient can be used in an application amount of approximately from 100 to 200 liters based on 10 a. In the case of the submerged application of granules containing from 5 to 15% of the active ingredient, the application amount is generally from 1 to 10 kg based on 10 a. In the case of the soil treatment, a solution containing from 5 to 1,000 ppm of the active ingredient can be used in an application amount of approximately from 1 to 10 liters based on 1 m2. In the case of the seed treatment, a solution containing from 10 to 1,000 ppm of the active ingredient can be used in an application amount of approximately from 10 to 100 ml based on 1 kg of the seed weight.
The present invention is described more illustratively in the following with reference to Example and Test Example, but the invention is not restricted by the following Example and Test Examples unless exceeding the gist thereof.